Colored cellulose material



Patented May 26, 1936 UNITED STATES PATENT OFFICE No Drawing. OriginalSerial No. 680,897.

tion April 30, 1934, Serial many August 19, 1932 4 Claims.

This application is divisional of my application Ser. No. 680,897, filedJuly 17, 1933.

In the said U. S. Patent application Ser. No.

680,897 there is described a process for direct pro- 5 duction of dyedregenerated cellulose material (viscose) consisting in incorporatinginto the viscous mass in any phase previous to coagulation the solutionof an ester-salt of a leuco vat dyestuff, inperforming the coagulationand finally in developing the dyeing in the regenerated cellulosematerial by acid oxidation.

As described in said application Serial No. 680,897 this process allowsalso the production of special dyeing effects.

It has now been found that in the same way also copper silk, obtained bydissolving cellulose by means of a solution of ammoniacal copper oxideand coagulating the solution with the aid of water or diluted acids oralkalies, whereby cellulose is re-formed, may be directly dyed.According to the present invention a solution of an ester-salt of leucovat dyestuff is added to the ammoniacal copper oxide cellulose solutionas a rule again in any phase of the process previous to coagulation.

Like in the case of viscose, a completely homogeneous mass is thusobtained, in which no precipitations or decompositions take place, whichmight adversely affect the subsequent spinning process and furtheroperations. This mass is then spun in the ordinary way and brought tocoagulation. The produced threads or materials are then subjected to theusual after-treatment for copper silk.

Development of the dyeing takes place by means of acid oxidation duringcoagulation, or by a suitable after-treatment of the regeneratedcellulose after coagulation. As cupric salts in the presence of an acidmay act as oxidizing agents, in many cases the copper salt, i. e. thecupric sulphate formed in the coagulation bath is sufficient to developthe dyeing (see U. S. Patent No. 1,917,101) In this case a furtheroxidative acid treatment is superfluous.

The same effects as in the case of viscose may generally also beattained with copper silk.

According to the present process it is also possible to apply on anykind of fabric an ammoniacal copperoxide cellulose mass to which anester-salt has been added, to bring the mass to coagulation, and todevelop the dyeing therein by means of acid oxidation during or aftercoagulation. In such a way particular effects are obtained, for exampledelustred or shiny relied ef- 55 fects, which are dyed fast.

application July 17, 1933, Divided and this applica- No. 723,276. InGer- The invention is illustrated, but not limited by the followingexamples:

Example 1 1 gr. of the ester-salt of leuco diamethoxyli- 5 benzanthroneis dissolved in 50 com. of lukewarm water and 20 com. of ammonia of 20ccm. of this solution are thoroughly mixed with 20 ccm. of an ammoniacalcopper oxide cellulose solution. This mixture is spunand co-agulated 0at C. in a bath containing 40% of sulphuric acid. The cellulose isregenerated. The copper sulphate formed in the acid coagulation bathacts as oxidizing agent and the green dyeing is developed during thecoagulation process. The thus 15 obtained threads are subjected to theusual aftertreatment for copper silk.

Example 2 1 gr. of the ester-salt of leuco dibenzpyrenequi- 20 none isdissolved in 50 ccm. of hot water. After cooling down, 20 ccm. ofammonia of 25% are added. 20 ccm. of this solution are thoroughly mixedwith 20 com. of a concentrated ammoniacal copper oxide cellulosesolution. The homogeneous mass is spun as usual and the threads arecoagulated at 40 C. in a bath containing 30% of caustic soda lye and ifnecessary small quantities of sugar, glucose, glycerine or any othersuitable ingredients. The threads are thoroughly rinsed 30 in watercontaining 20 grs. of sulphuric acid of 66 B. per litre. The ester-saltis not dissolved away from the fibre, neither in this stage nor in thefollowing coagulation bath. Finally the dyeing is developed by treatingthe material in a bath containing 36 grs. of sulphuric acid of 66 B., 3grs. of sodium nitrite, also 10 grs. of a solution of ammonium vanadate1 1000 per litre at a temperature of 20-40" C., or in a bath containing0.5 gr. of sodium bichromate or potassium bi- 40 chromate, 36 grs. ofsulphuric acid of 66 B., 20 grs. of a solution of ammonium vanadate111000 and 2 grs. of oxalic acid per litre. Thus one obtains artificialsilk threads of a bright, fast yellow.

What I claim is:-

1. A process for manufacturing colored cellulose material, whichconsists in adding to an ammoniacal copperoxide cellulose solution inany phase previous to coagulation a solution of an ester-salt of a leucovat dyestufi, performing the coagulation in known manner and developingthe dyeing in the regenerated cellulose by acid oxidation.

2. A process for manufacturing colored celammoniacal ester-salt of aleuco vat dyestuff, performing 'by treating the latter in a lulosematerial, which consists in adding to an copperoxide cellulose solutionan known manner and dethe regenerated cellulose bath containing bithecoagulation in a veloping the dyeing in chromate and acid. 7

3. A process for manufacturing colored cellulose material, whichconsists in adding to an ammoniacal copperoxide cellulose solutionprevi-' ous to coagulation a solution of an ester-salt of a leuco vatdyestuff, performing coagulation of the mass by pressing same into abath containing sulphuric acid, whereby owing to the formation of,coppersulphate acting in presence of acid as oxidinz agent,simultaneously with the coagulation the development of the dyeing in theregenerated cellulose takes place.,

4. The herein described colored cellulose mate- HENRY DOSNE.

